Hard resins



Patented Feb. 12, 1946 HARD RESINS Ferdinand P. Otto and Orland M. Iteifl, Woodbury, N. J., assignors to Socony-Vacuum Oil Company, Incorporated, a corporation of New 7 York No Drawing. Application September 15, 1943, Serial No. 502,508

4 Claims.

This invention has reference to a resinous composition of matter and is particularly concerned with a hard resin derived by mono-alkylation of aromatic bodies. This application is a continuation-in-part of our copending application Serial No. 428,580, filed December 19, 1941, now Patent No. 2,340,838.

In one respect, the present invention is related to the disclosure of Patent No. 2,191,498, issued February 27, 1940, to O. M. Reiff and the copending application of O. M. Reifi and J. J. Giammaria, Serial No. 427,588, filed January 21, 1942. Both of said disclosures are directed to aromatic compounds and mixtures of aromatic compounds which have substituted with long chain aliphatic radicals by a Friedel-Crafts reaction. In both instances, the aliphatic radical is preferably derived from petroleum wax. In these respects the present disclosure resembles the earlier disclosures noted above. As respects properties of the compositions concerned, the present invention relates to material of widely difierent nature. The products of the said patent are viscous liquids, soluble in lubricating oil, obtained by reaction of aromatics with chlorinated wax of about 14% chlorine content in such proportions as to polyalkylate the aromatic. The compositions described in the said application are plastic, rubber-like masses insoluble in hydrocarbon oils which result from reaction of an excess of chlorinated wax of high chlorine content (more than 25%) with aromatic compounds.

The products of this invention are hard resinous bodies soluble .in varnish resin solvents and are derived by reacting highly chlorinated wax. or other suitable aliphatic hydrocarbons, containing from about 40% to about 60% of chlorine with aromatic compounds and mixtures of such compounds in proportions to theoretically result in mono-alkylation of the aromatic. Pref-i erably, the aromatic reactant is used in substantial excess with respect to the chlorine content. By following the teachings of this invention as outlined above and described in greater detail below, the desired hard resin is obtained in a form admirably suited to the formation of fine coating compositions and for other purposes that will be apparent to those skilled in the art.

Of the two reactants, the chlorinated aliphatic seems to be the more important in affecting the characteristics of the final product. Good results are obtained with aromatic compounds in general by reaction with aliphatic hydrocarbons having upwards of about carbon atoms, which hydrocarbons have been chlorinated to the extent of about 40% to by weight. Preferably, an aliphatic compound of about 50% chlorine content is employed. Some variations in properties of the resins are noted with variations in the character of the aromatic used but the general properties of a hard resin are found within the above limits of chlorination when the proportions of reactants are such that there is present in the reaction mixture at least one mol of aromatic compound for each mol of combined chlorine in the chlorinated aliphatic. It is understood, of course, that other halogens than chlorine are available for the purposes of the invention and chlorine is discussed here as exemplary because it is the halogen generally used for the present purpose.

Although aliphatic compounds and mixtures of relatively low molecular weight, about 10 carbon atoms, are suitable, best results are obtained by the use of chlorinated petroleum waxes. Such waxes often contain some components of as few as 15 carbon atoms but the predominant portion of any such wax is usually composed of aliphatic hydrocarbons of 20 or more carbon atoms with an average of about 24 carbon atoms and an average molecular weight of about 350.

The hard, resin compositions derived from the reaction of chlorinated wax with aromatic compounds, might be more aptly described as arylated waxes because of their high aromatic content. Hard resins derived from phenol, for instance, have a combined phenol content of about 40%, the remainder of the molecule consisting of combined wax. A trace of chlorine is ordinarily present from incomplete reaction, but is not necessary for the formation of a hard resin.

The composition may be represented by the following general formulae which is not an attempt to give, however, an exact representation of the molecule. matic nuclei are represented by the phenyl radicals.

QQQQQQ Although a suflicient amount of the aromatic For simplicity, the difierent arov compounds is used in the reaction with the chlorinated wax that only monosubstitution of the aromatic nucleus should occur. theoretically, as represented by the first formula. apparently some polysubstltution also takes place as represented by the second formula. The compounds are rep- Moi ratio of D of aromatic to Molecular Resin combined Eff weight orine 2 50 1, 330 2 45 l, 030 4:3 50 550 4:3 50 l, 000 2 50 l, 250

Some chain formation would be expected to occur in the reaction of aromatic compounds with highly chlorinated waxes, in which case the following representation would be applicable, but the low molecular weights of the resins indicate little chaining of the arylated wax molecules.

. @QQQS The resins consist apparently of a mixture of the compounds represented by Formulae 1, 2 and 3. Because of the complexity of the mixtures, no attempt has been made to separate the resins into their constituents.

The different aromatic compounds are not equivalent in respect to the degree of chlorination of the wax required to produce a resin of the same degree of hardness and same melting point. Further, each aromatic compound can be reacted with chlor-wax of variable chlorine content to obtain products of different degrees of hardness and different melting points. For a chlorinated wax of diflferent chlorine content, a harder resin is derived from phenol than from aromatic hydrocarbons or aromatic ethers. In the following examples, a proportion of reactants is given whereby a resin of desirable degree of hardness and suitable melting point can be formed from different aromatic compounds. Examples only of unsubstituted hydroxyaromatic and aromatic hydrocarbons and aromatic ethers are given. Aromatic compounds containing low molecular weight alkyl substituents as in the case of toluene, xylene and methyl-naphthalene require reaction with chlorinated wax of higher chlorine content to obtain a resin of comparable hardness. Aromatic hydrocarbons having low molecular weight alkyl substituents of about five carbon atoms or less are contemplated as being in the scope of the invention.

EXAMPLE I Wax PnmwoLRnsm' chlorinated wax) 180 Zinc dust (for decolorizing) 300 duced, followed by gradual addition of the anhydrous AlCls ata temperature of about 60 C. withrapid stirring. The temperature of the mixture is gradually raised to about 175 C; during a 2-hour period and held at this point until the .evolution of HCl is complete, which will require about 4 hours.

The color of the reaction mixture can be lightened by the reducing action of zinc dust and dilute hydrochloric acid. This reduction is carried out by adding 300 grams of zinc dust and 100 cc. of water at about C. and stirring the mixture several hours. In'order to obtain a product of lighter color, it is desirable to add additional hydrochloric acid and continue the reduction several hours longer. As an aid to stirring the reaction mixture, it is desirable to add about 500 cc. of benzene before carrying out the reduction procedure. The reaction mixture is then filtered to remove excess-zinc, followed by water washing to remove acid, zinc chloride and aluminum chloride and then topping by heating to about 180 F. under diminished pressure to remove solvent and unreacted phenol. The product obtained is a light brown, hard resin of about 40 phenol content.

."This reaction procedure is applicable to the production of hard resins from hydroxyaromatic compounds in general. In the preparation of hardresins by the reaction of chlorinated wax with aromatic hydrocarbons and aromatic ethers, essentially the same reaction procedure is used. Less' A101: is required for the reaction. In the formation of hard resins from the following reaction mixtures, a top reaction temperature of about 150 C. is used in carrying out the Friedel- Crafts reaction. In the case of aromatic hydrocarbons boiling below 150 C., the Friedel-Crafts reaction is carried out at the boiling point of the aromatic compounds. Benzene, for instance, is converted to a hard resin by reaction with chlorinated wax at 80 C. Reaction mixtures for several resins within the scope of the invention are set out below.

EXAMPLE II WAxBsNznnx Ream Grams Chlorinated wax of 50% chlorine content 150 Benzene in excess of amount required for reaction) 330 A101: (20% by weight based on chlorwax) 30 Zinc dust (for decoiorizing) 100 m Grams Du, RESIN Grams Wax diphenyl of Example 111 100 Chlorinated wax of 50% chlorine content 150 i k 1 2g Diphenyl (50% in excess of amount required Bane-y P for reaction) 485 AlCls :30 Zinc dust (for decolorizing) 100 EXAMPLE IV Wax Narrrrnsnm Rssm Grams Chlorinated wax of 50% chlorine content--- 140 Naphthalene (100% in excess of amount required for reaction) 520 A1013 28 Zinc dust (for decolorizing) 100 EXAMPLE V Wax Drrmnoxmz Rrsm Grams Chlorinated wax of 50% chlorine content--- 100 Diphenyloxide (50% in excess of amount required for reaction) 348 AlCh 20 Zinc dust 100 The preparation of hard resins by the reaction of chlorinated paraffins (formed from parafllns of lower molecular weight than the wax range) with aromatic compounds, is carried out according to the procedures given in the foregoing reactions with chlorinated wax. The parafiinic material-is chlorinated to the same extent as is the case with wax and reacted with the various aromatic compounds in a similar manner.

EXAMPLE VI Rssm mom REACTION or CHLORINATED Sronnasn SOLVENT WITH Pmmor.

To a reaction mixture consisting of the chlorinated Stoddard solvent and phenol at 55 C. is added 45 grams 01' aluminum chloride. The temperature is then gradually raised to 175 C. and held there until the evolution of hydrogen chloride practically ceases, which will require about 2 hours. The reduction step then follows, consisting of dilution with 300 cc. of Stoddard solvent and the addition of zinc dust and 30 cc. of water, followed by refluxing the mixture for two hours. At this point, it is desirable to add 100 cc. of concentrated hydrochloric acid and continue the reduction for several hours longer to obtain improved decolorization. The product is then filtered, water washed until neutral and topped to 200 C. under diminished pressure (5 mm.) to remove the excess phenol and solvent. The product obtained is a dark-brown, hard resin. The resins prepared according to the foregoing examples are generally light brown in color but may be substantiall improved as to color by catalytic hydrogenation without materially aflecting their physical properties. Raney nickel is an excellent catalyst for this purpose and the color of the resins may be reduced to pale yellow by procedures set out below.

high pressure shaker-bomb along with 20% by weight of Raney nickel catalyst. The catalyst is prepared according to Covert and Adkins, J. A. C. S. 54, 4116, (1932). The initial pressure of hydrogen in the bomb is 1500 lbs. per square inch. The temperature is then raised to 500 F. and held there for a period of '7 hours during which time the pressure remains at 2700 lbs. per square inch. After cooling, the reaction mixture is removed from the bomb and filtered to remove catalyst. This is followed by topping to 175 C. under diminished pressure (5 mm.) to remove the solvent and to obtain the finished product.

EXAMPLEVIII V 7 Grams Wax phenol oi. Example I Dioxane 500 Raney nickel 20 The treatment is conducted in substantially the same fashion as in Example VII.

The alkylated aromatic compounds will undergo chemical reactions of which the parent aromatic compounds are capable, but with formation oi. products of different physical characteristics. The hard resins can be improved, for instance, by reaction with formaldehyde and other resinifying agents.

The hard resins vary from brown to pale yellow or colorless compounds depending upon the degree of reduction with hydrogen. The resins are soluble in varnish resin solvents and have been found to give highly desirable coatings.

Although the resin-forming reaction has been described as conducted with the use of an aluminum chloride catalyst, it will be understood that any suitable alkylation catalyst may be used, preferably a catalyst of the type employed in Friedel-Crafts reactions in general.

It will be seen that the invention is equally applicable to the use of pure aromatic compounds and mixtures of aromatics, with or without compounds other than aromatics, it being understood that proportions recited relate only to the reactive aromatic compounds and do not include diluents, impurities, and the like.

We claim:

1. A hard resinous light-colored composition of matter formed by reacting an aromatic compound of the class consisting of aromatic hydrocarbons having at least one incompletely substituted benzene ring and having no alkyl side chains of more than about five carbon atoms, in the presence of added heat, with a chlorinated petroleum wax containing about 40% to about 60% by weight of chlorine in a mol ratio of not less than one mol of said aromatic compound for each mol of combined chlorine in the presence of a Friedel-Crafts catalyst, and adding metallic zinc and Water to the reaction product to decolorize the same.

2. A hard resinous composition of matter formed by reacting an aromatic compoimd of the class consisting of aromatic hydrocarbons having at least one incompletely substituted benzene ring and having no alkyl side chains or more than of the class consisting oi aromatic hydrocarbons having at least one incompletely substituted benzene ring and having no alkyl side chains of more than about rive carbon atoms, in the presence of added heat, with a chlorinated petroleum wax asoaseo rlne in the presence or a Frledel-Craits catalyst. adding metallic zinc and water to the reaction product to decolorlze the same and further bydrogenating said product catalytically.

4. A hard resinous composition of matter formed by reacting an aromatic compound 0! the class consisting of aromatic hydrocarbons having at least one incompletely substituted benzene ring and having no alkyl side chains of more than about five carbon atoms, in the presence of added heat, with a chlorinated petroleum wax containin: about 50% by weight of chlorine in 9. mol ratio of not less than one mol of said aromatic compound for each mol of combined chlorine in containing about 50% by w ight of hlorin in a 15 the presence of a Friedel-Crafts catalyst. mol ratio or not less than one mol of said aro-' matic compound for each mol 0! combined chlo- FERDINAND P. OTTO. ORLAND NI. REIFF. 

